Surfactant Composition Method For Production Thereof And Cosmetic Comprising Said Composition

ABSTRACT

The invention relates to surfactant compositions made from esters or amides of the betaine glycine, produced by reaction of the glycine betaine with a sulphonic acid and an alcohol or a fatty-chain amine derived from vegetable oils. The invention further relates to a cosmetic comprising said surfactant composition, in particular, liquid soap, bath foam, shower gel or shampoo.

The invention relates to surfactant compositions.

From detergents to cosmetic formulations, via emulsification, thechemistry of surfactants supplies an extremely varied range of productswhich are nowadays indispensable to our daily life. Although the marketfor cationic amphiphiles is quantitatively smaller than that for anionicor non-ionic amphiphiles, representing a percentage of the worldwideproduction of less than 10%, it is nevertheless very extensive andcovers numerous applications.

Due to their toxicity, certain surfactants such as the salts ofdimethyldialkyl ammonium which are present in most textile conditioners,are restricted in use, and have even been abandoned in some Europeancountries such as Germany and the Netherlands. Under the pressure ofenvironmental considerations, the manufacturers of surfactants arehaving to propose not only methods compatible with these newrequirements, but also less polluting products which are morebiodegradable and cause the lowest possible pollution of theenvironment. Added to the environmental constraints is a considerablecommercial argument, of using what is “natural”. To respond to thedemands of the consumer, and at pains to find products having a “greenimage”, the manufacturers are currently researching new structures andare naturally turning to the use of raw materials of agriculturalorigin.

If, for the lipophilic part of these molecules, competition is wellestablished between the petrochemical substances and the oleochemicalsubstances, it is not yet really engaged as far as the hydrophilic partof these molecules is concerned. The direct use of naturaltriglycerides, such as triglycerol ricinoleate [U.S. Pat. No. 4,857,310(The Gillette Company)], makes it possible to have easy access tocationic amphiphilic compounds. But the diversification of thestructures is effected also by modification of the polar head. Cationicsurfactants, derived in particular from glucuronic acid and galacturonicacid [DE 195 39 845 (Henkel KgaA)] or with a starch base comprising asugar entity derived from alkyl polyglycosides (APG) [WO 90 15809(Henkel KgaA)] have been proposed. Another type of surfactant isappearing. This involves molecules having a saponifiable ester functionbetween the fatty chain and the quaternary ammonium function, such asammonium chlorides [U.S. Pat. No. 5,527,477 (Lever Brothers Company)].Being easily hydrolysable, the betaine esters are also currentlystirring up strong interest. Various derivatives have been synthesised([WO 96 09276 (The Procter and Gamble Company:], [U.S. Pat. No.5,527,477 (Lever Brothers Company)], intended for applications such astextile conditioners.

Betaine glycine, a cheap natural substance, forms a raw material ofchoice for the production of surfactant agents. Representing 27% byweight of sugar-beet molasses, obtained after extraction of the sucrose,it remains currently a by-product of the sugar industry. The grafting onto the betaine glycine of fatty alcohols and fatty acids ([U.S. Pat. No.2,888,383 (International Minerals and Chemical Corporation)], [EP 0 750904 A1 (Wella-AG)] makes it possible to obtain amphiphilic cationicmolecules without the conventional stage of quaternisation of a tertiaryamine using methylation agents which are generally toxic.

The present invention aims to propose means of rapidly obtainingmixtures of a perfectly defined composition with a base of esters oramides of the betaine glycine obtained in the form of reactional rawmaterials or by washing of the reactional raw materials with organicsolvents. The methods of synthesis used are simple, efficient, respectthe environment without solvent or pollutant waste, are easy to converton an industrial scale and allow the upgrading of a by-product of thesugar industry and of vegetable oils of domestic origin (e.g. colza orsunflower) which are rich in fatty chains with a high carboncondensation (stearic, oleic, linoleic, linolenic, arachidic, gadolic,behenic, erucic chains) which are even less re-used compared tooleaginous resources of tropical origin (e.g. palm, cabbage tree orcopra) which are rich in caprylic, capric, lauric, myristic or palmiticchains.

The 18-atom fatty chains of carbons derived from domestic vegetable oilsare known for their emulsifying properties and the compositionsaccording to the invention cover a large range of potential applicationsin the field of emulsification, as well as in the petrol industry, themining industry, the paint, pigment and varnish industry or in thebuilding and civil engineering industry.

The invention also relates to the use of the mixtures mentioned above byway of detergent, emulsifying or foaming agents for applications in thecosmetics field.

The invention relates in particular to a surfactant compositioncomprising:

at least one compound of formula (1)X⁻(CH₃)₃N⁺—CH₂—CO-Z-R  (1)and at least one compound selected from those with formulae (2), (3) and(4)RZH  (2)XH  (3)X⁻(CH₃)₃N⁺—CH₂—CO—OH  (4)X being a sulphonate radical,R being a monovalent radical of formula C_(2n)H_(2(2n-m)+1) containing2n atoms of carbon and m double bonds, with 9≦n≦11, 0≦m≦3 if n=9 and0≦m≦1 if n>9, andZ being selected from an atom of oxygen and a —NH— group, a compound offormula XH being combined if necessary with at least one compound offormula RNH₂ in order to form at least one compound of formula X⁻RN⁺H₃.

Advantageously, the composition according to the invention comprisesvirtually exclusively compounds of the said formulae (1), (2), (3) and(4).

Optional additional or alternative features of the invention areindicated below:

m=0 and the compounds forming the composition are as follows, in thepercentages by weight indicated: X⁻(CH₃)₃N⁺—CH₂—CO—O—R 50 ± 10 ROH 19 ±10 XH 23 ± 10 X⁻(CH₃)₃N⁺—CH₂—CO—OH 0 to 18.

m=0 and the compounds forming the composition are the following, in thepercentages by weight indicated: X⁻(CH₃)₃N⁺—CH₂—CO—O—R 72 ± 10 ROH 0 to20 XH 0 to 18 X⁻(CH₃)₃N⁺—CH₂—CO—OH 0 to 20

m=0 and the compounds forming the composition are the following, in thepercentages by weight indicated: X⁻(CH₃)₃N⁺—CH₂—CO—O—R 80 ± 10 ROH 20 ±10.

m=0 and the compounds forming the composition are the following, in thepercentages by weight indicated: X⁻(CH₃)₃N⁺—CH₂—CO—O—R 70 ± 10 ROH 26 ±10 XH 0 to 14.

m>0 and the compounds forming the composition are the following, in thepercentages by weight indicated: X⁻(CH₃)₃N⁺—CH₂—CO—O—R 48 ± 10 ROH 36 ±10 XH 14 ± 10 X⁻(CH₃)₃N⁺—CH₂—CO—0H 0 to 12.

m=0 and the compounds forming the composition are the following, in thepercentages by weight indicated: X⁻(CH₃)₃N⁺—CH₂—CO—NH—R 58 ± 10 X⁻RN⁺H₃35 ± 10 X⁻(CH₃)₃N⁺—CH₂—CO—OH 0 to 20.

m>0 and the compounds forming the composition are the following, in thepercentages by weight indicated: X⁻(CH₃)₃N⁺—CH₂—CO—NH—R 56 ± 10 X⁻RN⁺H₃31 ± 10 RNH₂ 0 to 18 X⁻(CH₃)₃N⁺—CH₂—CO—OH 0 to 15.

-   -   X is selected from the radicals methanesulphonate,        paratoluenesulphonate and camphosulphonate.

The invention also has the object of a method of preparing a compositionsuch as defined above in which betaine glycine is reacted with asulphonic acid and a compound of the formula ROH in the absence of othersolvents, the molar ratio of the sulphonic acid to betaine glycine beingcomprised between 2 and 3 and the molar ratio of the compound ROH tobetaine glycine being between 1 and 1.5.

The method according to the invention may comprise at least some of thefollowing features:

-   -   The reaction is carried out at a temperature of between 130 and        140° C. for 6 to 8 hours.    -   The reaction is carried out under reduced pressure, preferably        of between 50 and 100 mbar.    -   m=0 and the reactional mixture is treated with an organic        solvent capable of dissolving preferably the compounds other        than the X⁻(CH₃)₃N⁺—CH₂—CO—O—R contained therein so as to obtain        a precipitate enriched in X⁻(CH₃)₃N⁺—CH₂—CO—O—R.    -   the organic solvent is selected from diethyl ether, ethanol and        n-butanol.    -   The betaine glycine is reacted with a sulphonic acid and the        n-butanol in the absence of other solvents, the molar ratio of        the sulphonic acid to the betaine glycine being between 1 and        1.3 and the molar ratio of the n-butanol to the betaine glycine        between 2 and 4 in order to form water and the n-butylic ester        sulphonate of betaine glycine which is reacted—after having        eliminated the water and the n-butanol—with the compound of        formula RNH₃, the molar ratio of this compound to the betaine        glycine being between 1 and 1.2.    -   The reaction of the betaine glycine with the sulphonic acid and        the n-butanol is carried out at a temperature of between 130 and        140° C., upon reflux of the n-butanol, for 3 to 5 hours under        atmospheric pressure so as to realise azeotropic elimination of        water.    -   Before the compound of formula RNH₂ is added, a strong        encumbered organic base is added, in particular dibutylamine,        the molar ratio of the said base to the betaine glycine being        between 0.1 and 0.4.    -   m=0 and the reactional mixture is treated with an organic        solvent capable of dissolving preferably the compound RNH₂ so as        to obtain a precipitate enriched with X⁻(CH₃)₃N⁺—CH₂—CO—NH—R.    -   The organic solvent is diethyl ether.    -   The sulphonic acid is selected from methanesulphonic,        paratoluenesulphonic and camphosulphonic acid.

The invention also aims at a cosmetic, in particular a liquid soap, bathfoam, shower gel or shampoo and in particular acid shampoo, comprisingfrom 0.2 to 60% and preferably from 10 to 45% by weight of a compositionsuch as defined above and from 99.8 to 40% and preferably from 90 to 55%by weight of excipients appropriate for cosmetology.

Advantageously in the cosmetic according to the invention, theexcipients are selected from thickeners, texturisers, conditioningagents, softeners, complexing agents, perfumes, pearlising agents,preservatives, acidifiers and purified water, and comprise astexturisers diethylanolamides of fatty acids, in particulardiethanolamide of copra, with a content not exceeding 10% by weight ofthe cosmetic.

A first type of composition according to the invention has a base offatty esters of the betaine glycine.

The method of preparing these mixtures consists in reacting the betaineglycine with 2 to 3 molar equivalents of a sulphonic acid and 1 to 1.5molar equivalent of a saturated fatty alcohol of the type C_(18:0),C_(20:0) or C_(22:0) or of a non-saturated fatty alcohol of the typeC_(18:1), C_(18:2), C_(18:3), C_(20:1) or C_(22:1), the numbers beforeand after the sign “:” representing respectively the number of carbonatoms and the number of double carbon-carbon bonds. The esterificationreaction of the betaine glycine in the zwitterionic form requiresprevious protonation of its carboxylate function. The acid of thebetaine reacts with the fatty alcohol in the presence of the excess ofacid in order to lead to the corresponding esters. This reaction iscarried out in the absence of any solvent, the fatty alcohol usedforming both the reagent and the medium.

Preferably, the reaction is carried out at a temperature of between 130and 140° C. for 6 to 8 hours. The water formed during the reaction iseliminated continuously under reduced pressure, preferably of between 50and 100 mbar.

The reactional raw materials resulting from carrying out of the methoddescribed make it possible to obtain mixtures formed of fatty ester ofthe betaine glycine, residual fatty alcohol, residual sulphonic acid andresidual betaine glycine present in the protonated form, theseconstituents having the coefficients a, b, c and d respectively, thevalues of which can be determined by spectroscopy of RMN ¹H.

When a saturated fatty alcohol is used in the reaction, rapid partialpurification based on the difference of solubility between the fattyalcohol and the synthesised ester consists in the recovery of thereactional raw material by means of organic solvents such as diethylether, ethanol or n-butanol at the end of the reaction. The ester,insoluble in solvents such as diethyl ether or ethanol or partiallysoluble in butanol, precipitates and the fatty alcohol partiallydissolves. By filtration, powders are obtained which are mainly formedof ester whose composition by mass may be determined by spectroscopy ofRMN ¹H.

According to the organic solvent used to wash the reactional rawmaterials, the coefficients a, b, c and d vary. The use of alcohols withshort carbon chains makes it possible to obtain mixtures where thecoefficients c and d are roughly equal to zero, the use of diethyl ethermakes it possible to obtain mixtures having a low residual rate ofsaturated fatty alcohol (b). The excellent solubility of non-saturatedfatty alcohols and of their corresponding esters in organic solventsdoes not make it possible to apply the method described, and the onlyones that can be obtained are mixtures in the form of reactional rawmaterials.

It is possible to purify fatty esters of betaine glycine bychromatography of the mixtures according to the invention on a column ofsilica gel by means of ternary polar eluants of the type ethylacetate/isopropanol/water.

The fatty esters of betaine glycine have a hydrolysable function betweenthe fatty chain and the quaternary ammonium. The study of theirbehaviour in an aqueous medium makes it possible to contribute animportant fact concerning their biodegradability. The stability of thederivatives is tested by chromatography in a gaseous phase by meteringthe fatty alcohol produced during the hydrolysis reaction in an aqueousbuffer solution whose pH-value is fixed at different values.

The measurement of the surface tensions and critical micellarconcentrations proves that the synthesised derivatives have amphiphilicproperties which make it possible to use the mixtures proposed assurfactant agents (in particular as emulsifiers).

The other family of mixtures according to the invention has a base offatty amide of betaine glycine.

The method of preparing these mixtures in the first instance uses thereaction of the betaine glycine with 1 to 1.3 molar equivalent of asulphonic acid and 2 to 4 molar equivalents of n-butanol forming boththe reagent and the medium in order to form the n-butyl ester in theform of intermediate sulphonate. Preferably, the first stage is carriedout at a temperature of between 130 and 140° C., at the reflux of then-butanol, for 3 to 5 hours and at atmospheric pressure. The slowdistillation of the n-butanol makes it possible to eliminateazeotropically the water formed during the reaction. To the mixturecooled to ambient temperature is then added 1 to 1.2 molar equivalent ofa saturated fatty amine of the type C_(18:0), C_(20:0) or C_(22:0) or ofa non-saturated fatty amine of the type C_(18:1), C_(18:2), C_(18:3),C_(20:1) or C_(22:1). The reactional medium is heated under reducedpressure to eliminate the n-butanol and aminolysis is carried out for 2to 4 hours at 130° C. between 50 and 100 mbar.

The formation of the salt of fatty amine resulting from the protonationof the amine by the excess of acid can be limited by the use of 0.1 to0.4 molar equivalent of a strong, encumbered organic base such asdibutylamine added before the fatty amine.

The reactional raw materials resulting from carrying out the methoddescribed make it possible to obtain mixtures formed of fatty amide ofbetaine glycine, sulphonate of the fatty amine used during aminolysis, alow residue of fatty acid and of residual betaine glycine present in aprotonated form, these constituents having coefficients e, f, g and hrespectively, the values of which can be determined by spectroscopy ofRMN ¹H.

When a saturated fatty amine is used in the reaction, rapid partialpurification based on the difference of solubility between the fattyamine and the synthesised amide consists in the recovery of thereactional raw material by means of diethyl ether at the end of thereaction. The amide and the salt of the fatty amine which are insolublein the solvent precipitate and the fatty amine dissolves. By filtration,powders are obtained which are mainly formed of amide whose compositionby mass can be determined by spectroscopy of RMN ¹H. The use of diethylether makes it possible to obtain mixtures having a residual proportionof saturated fatty amine (g) roughly equal to zero. The recovery of thereactional raw materials by means of alcohols with short carbon chainssuch as ethanol or n-butanol leads to dissolving of the residues.

The excellent solubility of non-saturated fatty amines and of thecorresponding amides in organic solvents does not make it possible toapply the method described and the only ones obtainable are mixtures inthe form of reactional raw materials.

The fatty amides of the betaine glycine can be purified bychromatography of the mixtures according to the invention on a column ofsilica gel by means of ternary polar eluants of the type ethylacetate/isopropanol/water. The measurement of the surface tensions andcritical micellar concentrations proves that the synthesised amidederivatives also have amphiphilic properties which make it possible touse the mixtures proposed as surfactant agents (in particular asemulsifiers).

The ester and amide derivatives of the betaine glycine have goodsurfactant properties with surface tensions and critical micellarconcentrations which are relatively low. These derivatives according tothe invention have surface tensions of the same order as the referencesurfactants such as alkyl polyglucosides or sodium dodecyl sulphate(known by the registered Trade Mark SDS), which is widely used inindustry. Compared to these commercial derivatives, critical micellarconcentrations are obtained which are lower, which has a majoradvantage. In fact, less product is needed to obtain micellar solutions.

In the presence of water, these derivatives hydrate to varying degreesaccording to the condensation of carbon in the chains. They thus make itpossible to homogenise a water-oil mixture by acting on the interactionswhich are both hydrophilic (surfactant/water) and lipophilic(surfactant/oil). They allow the formulation of very stable emulsions,including for low concentrations of surfactant, for variablewater/surfactant/oil ratios and for different types of oil (inparticular fatty acid methyl esters).

These single-chain surfactants are found to be very advantageous due totheir foaming capacity and the stability of the foams formed, since theyare as effective as SDS (registered Trade Mark), hence their use in theformulation of foaming products such as shampoos, liquid soaps, showergels and bath foams.

Thus, the invention supplies cosmetics containing 0.2 to 60% andpreferably 10 to 45% by weight of a surfactant composition according tothe invention and from 99.8 to 40% and preferably 90 to 55% by weightexcipients.

Such a cosmetic may be a liquid soap, a bath foam, a shower gel or ashampoo, in particular an acid shampoo having excellent foamingproperties, associated with excellent volumising properties, giving bodyto the user's hair. An acid shampoo is for example composed of 10 to 45%by weight of a surfactant composition according to the invention with abase of fatty esters of the betaine glycine and 90 to 55% additives. Theadditives may be thickeners, texturisers, such as diethanolamide offatty acids, in particular diethanolamide of copra which is incorporatedat a level of 0-10% by weight in the formulation, conditioning agents,softeners, complexing agents and finally perfumes, pearlising agents,preservatives, acidifiers in sufficient quantity, and purified water.

The invention is further illustrated by the following examples.

EXAMPLE 1 Synthesis of Octadecyl Betaine Mesylate and Preparation of theCorresponding Mixtures

To a suspension of betaine glycine (25 g, 0.213 mole) inmethanesulphonic acid (53.3 g, 0.555 mole) is added octadecanol (69.3 g,0.256 mole). The mixture thus obtained is heated progressively to 130°C. under reduced pressure (50 to 60 mbar) to eliminate the water formedduring the esterification reaction. The mixture becomes homogeneous atthe end of 1 to 2 hours' stirring at the same temperature. After 7hours, the medium is cooled to ambient temperature.

Method A: The reactional raw material obtained (143 g) forms a firstcomposition according to the invention.

Method B: The reactional raw material obtained is washed with diethylether (600 ml) until complete recovery of the residue. The precipitateobtained is then filtered on Büchner and rinsed several times with thesame solvent (2 □.200 ml). The product is dried in a vacuum and 96 g ofa white powder is eventually obtained.

Method C: The reactional raw material obtained is washed with ethanol(800 ml) until complete recovery of the residue. The precipitateobtained is then filtered on Büchner and rinsed several times with thesame solvent (2 □.200 ml). The product is dried in a vacuum and 87 g ofa white powder is eventually obtained.

Method D: The reactional raw material obtained is washed with n-butanol(900 ml) until complete recovery of the residue. The precipitateobtained is then filtered on Büchner and rinsed several times with thesame solvent (2 □.200 ml). The product is dried in a vacuum and 42 g ofa slightly grey powder is eventually obtained.

The composition of each mixture is evaluated by RMN of the proton bymeasuring the integration ratios between the different components. TheRMN spectra are recorded on a Bruker ARX-400 apparatus. The RMN ¹Hspectra are obtained at 400 MHz (s=singlet, d=doublet, t=triplet,m=multiplet, I=wide). The RMN ¹³C spectra are obtained at 100 MHz in thedecoupling mode of the proton. The chemical displacements are given inppm relative to internal TMS (δ scale) and the coupling constants (J) inHz.

RMN ¹H of the reactional raw material (CDCl₃+CD₃OD, 1/1):

δ 0.84 (t, CH₃ ester+CH₃ alcohol, ³J 6.7 Hz), 1.22 (sl, (CH ₂)₁₅CH₃ester+(CH ₂)₁₅CH₃ alcohol), 1.51 (m, CH ₂CH₂O alcohol), 1.65 (m, CH₂CH₂O ester), 2.73 (s, CH₃SO₃ ⁻ ester+CH₃SO₃ ⁻ acid+CH₃SO₃ ⁻ betaineglycine), 3.29 (s, (CH₃)₃ ester+(CH₃)₃ betaine glycine), 3.51 (t, CH₂ CH₂O alcohol, ³J 6.7 Hz), 4.20 (t, CH₂ CH ₂O ester, ³J 6.8 Hz), 4.25 (s,CH₂CO betaine glycine), 4.33 (s, CH₂CO ester).

Composition of the Mixtures Method of treatment a b c d A 50 19 23 8 B72 10 8 10 C 80 20 0 0 D 70 26 4 0a, b, c and d are expressed as a percentage by mass.

The reactional raw material or the product obtained by the method oftreatment B is chromatographed on a column of silica gel (ethylacetate-isopropanol-water (6.2:3:0.8)) in order to give about 70 g ofoctadecyl betaine mesylate.

C₂₄H₅₁NO₅S; M=465.74 g/mole

White solid; yield: ≈70%

CCM: R_(f) 0.39 (ethyl acetate-isopropanol-water (6:3:1))

IR (Nujol) ν (cm⁻¹): 1755 (C═O)

RMN ¹H (CDCl₃+CD₃OD, 1/1):

δ 0.83 (t, 3H, CH₃, ³J 6/7 Hz), 1.22 (sl, 30H, (CH ₂)₁₅CH₃), 1.65 (m,2H, CH ₂CH₂O), 2.70 (s, 3H, CH₃SO₃ ⁻), 3.29 (s, 9H, (CH ₃)₃), 4.20 (t,2H, CH₂ CH ₂O, ³J 6.7 Hz), 4.34 (s, 2H, CH₂CO).

RMN ¹³C (CDCl₃+CD₃OD, 1/1):

δ 14.33 (CH₃), 23.17, 26.22, 28.82, 29.71, 29.88, 30.02, 30.08, 30.19,32.45 (CH₂ aliph.), 39.50 (CH₃SO₃ ⁻), 54.18 ((CH₃)₃), 63.46 (CH₂ CH₂O),67.27 (CH₂CO) 165.24 (CH₂ CO).

EXAMPLE 2 Synthesis of 9-octadecenyl Betaine Mesylate and Preparation ofthe Corresponding Mixture

To a suspension of betaine glycine (30 g, 0.256 mole) inmethanesulphonic acid (61.523 g, 0.64 mole) is added oleic alcohol(96.25 g, 0.359 mole). The mixture thus obtained is heated progressivelyto 130° C. under reduced pressure (50 to 100 mbar) in order to eliminatethe water formed during the esterification reaction. The mixture becomeshomogeneous at the end of 1 to 2 hours' stirring at the sametemperature. After 7 hours, the medium is cooled to ambient temperature.The reactional raw material obtained (210 g) forms a compositionaccording to the invention.

RMN ¹H of the reactional raw material (CDCL₃):

δ 0.83 (t, CH₃ ester+CH₃ alcohol, ³J 6.8 Hz), 1.22 (sl, CH₃(CH₂)₆CH₂CH═CH CH₂(CH ₂)₅CH₂CH₂O ester+alcohol), 1.50 (m, CH ₂CH₂Oalcohol), 1.64 (m, CH ₂CH₂O ester) 1.94 (m, CH ₂CH═CHCH ₂ ester+CH₂CH═CHCH ₂ alcohol), 2.74 (s, CH₃SO₃ ⁻ ester+CH₃SO₃ ⁻ acid+CH₃SO₃ ⁻betaine glycine), 3.30 (s, (CH₃)₃ ester+(CH₃)₃ betaine glycine), 3.51(t, CH₂ CH ₂O alcohol, ³J 6.7 Hz), 4.19 (t, CH ₂CH₂O ester, ³J 6.8 Hz),4.24 (s, CH₂CO betaine glycine), 4.32 (s, CH₂CO ester), 5.30 (m, CH₂CH═CHCH₂ ester+CH₂ CH═CHCH₂ alcohol).

Composition of the Mixture Method of treatment a b c d A 48 36 14 2a, b, c and d are expressed as a percentage by mass.

The reactional raw material is chromatographed on a column of silica gel(ethyl acetate-isopropanol-water (6.2:3:0.8 then 6:3:1)) to give about100 g 9-octadecenyl betaine mesylate.

C₂₄H₄₉NO₅S; M=463.72 g/mol

Yellow viscous oil; yield: ≈85%

CCM: Rf 0.4 (ethyl acetate-isopropanol-water (6:3:1))

IR (Nujol) ν (cm⁻¹): 1755 (C═O); 1650 (C═C)

RMN ⁻¹H (CDCl₃):

δ 0.83 (t, 3H, CH₃, ³J 6.8 Hz), 1.22 (sl, 22H, CH₃(CH ₂)₆ CH₂CH═CHCH₂(CH ₂)₅ CH₂CH₂O), 1.64 (m, 2H, CH ₂CH₂O), 1.94 (m, 4H, CH ₂CH═CHCH₂), 2.71 (s, 3H, CH₃SO₃ ⁻), 3.30 (s, 9H, (CH₃)₃), 4.19 (t, 2H, CH₂ CH₂O, ³J 6.8 Hz), 4.32 (s, 2H, CH₂CO), 5.31 (m, 2H, CH₂ CH═CHCH₂).

RMN ¹³C (CDCl₃):

δ 14.21 (CH₃), 22.90, 25.89, 27.40, 28.49, 29.38, 29.52, 29.62, 29.73,29.86, 29.91, 29.96, 32.13, 32.81 (CH₂aliph.), 39.27 (CH₃SO₃ ⁻), 54.09((CH₃)₃), 63.22 (CH₂ CH₂O), 67.09 (CH₂CO), 129.93, 130.24 (CH₂CH═CHCH₂), 164.88 (CH₂CO).

EXAMPLE 3 Synthesis of Betainylaminooctadecane Mesylate and Preparationof a Corresponding Mixture

A suspension of betaine glycine (25 g, 0.213 mole) in n-butanol (59 ml,0.64 mole) was formed in the presence of methanesulphonic acid (22.56 g,0.235 mole). The reactional mixture is brought to the reflux point ofn-butanol at 140° C. The medium becomes homogeneous at the end of 3 to 4hours' stirring. To the mixture cooled to ambient temperature is addeddibutylamine (8.27 g, 0.064 mole) and the medium is stirred for about 15minutes. Octadecylamine is then added (69 g, 0.256 mole), then then-butanol is eliminated under reduced pressure. Aminolysis is carriedout at 130° C. under reduced pressure (50 to 100 mbar). After 3 hours,the medium is cooled to ambient temperature. The reaction raw materialobtained is washed with diethyl ether (1600 ml) until complete recoveryof the residue. The precipitate obtained is then filtered on a Büchnerand rinsed several times with the same solvent (2 □.200 ml). The productis dried in a vacuum and 98 g of a white powder having a surfactantcomposition according to the invention is eventually obtained.

RMN ¹H of the mixture obtained (CDCL₃+CD₃OD, 1/1):

δ 0.90 (t, CH₃ amide+CH₃ amine salt, ³J 6.7 Hz), 1.29 (sl, (CH ₂)₁₅CH₃amide+(CH ₂)₁₅CH₃ amine salt), 1.56 (m, CH ₂CH₂NH amide), 1.67 (m, CH₂CH₂NH₃ ⁺ amine salt), 2.78 (s, CH₃SO₃ ⁻ amide+CH₃SO₃ ⁻ aminesalt+CH₃SO₃ ⁻ betaine glycine), 2.91 (m, CH₂ CH ₂NH₃ ⁺ amine salt), 3.26(m, CH₂CH₂NH amide), 3.30 (s, (CH₃)₃ betaine glycine), 3.35 (s, (CH₃)₃amide), 3.82 (s, CH₂CO betaine glycine), 4.10 (s, CH₂CO amide).

Composition of the Mixture Method of treatment e f g h B 58 35 0 10

e, f, g and h are expressed as a percentage by mass of the mixture.

The product obtained by the method of treatment B is chromatographed ona column of silica gel (ethyl acetate-isopropanol-water (6:3:1 then5:3:2) to give about 58 g betainylaminooctadecane mesylate.

C₂₄H₅₂N₂O₄S; M=464.75 g/mol

White solid; yield: ≈60%

CCM: Rf 0.5 (ethyl acetate-isopropanol-water (5:3:2))

IR (Nujol) ν (cm⁻¹): 1680 (Amide I); 1578 (Amide II)

RMN ¹H (DMSO):

δ 0.86 (t, 3H, CH₃, ³J 6.8 Hz), 1.25 (sl, 30H, (CH ₂)₁₅CH₃), 1.45 (m,2H, CH ₂CH₂NH), 2.37 (s, 3H, CH₃SO₃ ⁻), 3.10 (m 2H, CH₂ CH ₂NH), 3.21(s, 9H, (CH₃)₃, 4.05 (s, 2H, CH₂CO), 8.64 (s, 1H, NH).

RMN ¹³C (DMSO):

δ 13.40 (CH₃) 21.63, 24.22, 26.01, 28.27, 28.59, 30.88 (CH₂aliph.),38.50, (CH₂NH), 39.42 (CH₃SO₃ ⁻), 53.35 ((CH₃)₃), 64.24 (CH ₂CO), 162.66(CH₂ CO).

EXAMPLE 4 Synthesis of betainylaminooctadecenyl mesylate and Preparationof the Corresponding Mixture

A suspension of betaine glycine (25 g, 0.213 mole) in n-butanol (59 ml,0.64 mole) was formed in the presence of methanesulphonic acid (22.56 g,0.235 mole). The reactional mixture is brought to the reflux point ofn-butanol at 140° C. The medium becomes homogeneous at the end of 3 to 4hours' stirring. To the mixture cooled to ambient temperature is addedoleic amine (68.5 g, 0.256 mole), then the n-butanol is eliminated underreduced pressure. Aminolysis is carried out at 130-140° C. under reducedpressure (50 to 100 mbar). After 3 hours, the medium is cooled toambient temperature. The reactional raw material obtained (114 g) formsa surfactant composition according to the invention.

RMN 1H of the reactional raw material (CDCl₃):

δ 0.86 (t, CH₃ amide+CH₃ amine salt+CH₃ amine, ³J 6.7 Hz), 1.29 (sl,CH₃(CH ₂)₆CH₂CH═CHCH₂(CH ₂)₅CH₂CH₂N amide+amine salt+amine+CH ₂CH₂NH₂amine), 1.52 (m, CH ₂CH₂NH amide), 1.61 (m, CH ₂CH₂NH₃ ⁺ amine salt),1.98 (m, CH ₂CH═CHCH ₂ amide+amine salt+amine), 2.67 (t, CH₂ CH ₂NH₂amine, ³J 6.8 Hz), 2.73 (s, CH₃SO₃ ⁻ amide+CH₃SO₃ ⁻ amine salt+CH₃SO₃ ⁻betaine glycine), 2.87 (m, CH₂ CH ₂NH₃ ⁺ amine salt), 3.21 (m, CH₂ CH═NHamide), 3.27 (s, (CH₃)₃ betaine glycine), 3.31 (s, (CH₃)₃ amide), 3.77(s, CH₂CO betaine glycine), 4.08 (s, CH₂CO amide), 5.30 (m, CH₂ CH═CHCH₂amide+amine salt+amine).

Composition of the Mixture Method of treatment e f g h A 56 31 8 5e, f, g and h are expressed as a percentage by mass of the mixture.

The reactional raw material is chromatographed on a column of silica gel(ethyl acetate-isopropanol-water (6:3:1 then 5:3:2)) in order to giveabout 64 g of betainylaminooctadecenyl mesylate.

C₂₄H₅₀N₂O₄S; M=462.74 g/mol

White solid; yield: ≈65%

CCM: Rf 0.52 (ethyl acetate-isopropanol-water (5:3:2))

IR (Nujol) ν (cm⁻¹): 1678 (Amide I); 1576 (Amide II) 1640 (C═C)

RMN ¹H (DMSO):

δ 0.84 (t, 3H, CH₃, ³J 6.7 Hz), 1.23 (sl 22H, CH₃(CH ₂)₆CH₂CH═CHCH₂(CH₂)₅CH₂CH₂NH), 1.40 (m, 2H, CH ₂CH₂NH), 1.97 (m, 4H, CH ₂CH═CHCH ₂), 2.33(s, 3H, CH₃SO₃ ⁻), 3.08 (m, 2H, CH₂ CH ₂NH), 3.20 (s, 9H, (CH₃)₃), 4.07(s, 2H, CH₂CO), 5.31 (m, 2H, CH₂ CH═CHCH₂), 8.61 (s, 1H, NH).

RMN ¹³C (DMSO):

δ 14.08 (CH₃), 22.20, 26.43, 26.65, 26.69, 28.69, 28.73, 28.80, 28.92,29.96, 29.17, 29.22, 31.38, 32.04 (CH₂aliph.), 38.66 (CH₂NH), 39.78(CH₃SO₃ ⁻), 53.25 ((CH₃)₃), 63.86 (CH ₂CO), 129.74, 129.75 (CH₂CH═CHCH₂), 163.19 (CH₂ CO).

The physico-chemical properties of certain derivatives according to theinvention are given below.

Measurement of Surface Tension and Critical Micellar Concentrations

The tensiometric measurements were carried out with a drop tensiometeroperating by the method of the rising drop (TRACKER tensiometer, I.T.CONCEPT). Amphiphilic compounds γcmc (mN/m) CMC (M) Esters C_(18:0) 37.2  8.10⁻⁴ C_(18:1) 36.6   1.10⁻⁴ Amides C_(18:0) 36.0 1.4.10⁻⁴ C_(18:1)36.2 1.2.10⁻⁴ Examples of widely used Surfactants APG (C₁₂) 33.02.6.10⁻⁴ SDS (C₁₂) 30.0   8.10⁻³Stability of Fatty Esters of the Betaine Glycine in an Aqueous Medium

The stability of octadecyl betaine mesylate is observed in an aqueousbuffer solution whose pH-value is fixed to various values between 3 and9. The initial concentration of surfactant in the buffer samples is3.4.10⁻² Mole/l. The fatty alcohol released during the hydrolysisreaction is extracted by diethyl ether. After each extraction, thesamples are centrifuged (10,000 rpm, 10 minutes) to “break” theemulsions formed. The etherised solution is then analysed bychromatography in a gaseous phase on an apolar column AT1(polydimethylsiloxane) by using the n-dodecanol as an internal standard.The conditions applied are the following: injector at 320° C., detectorat 330° C. and temperature gradient in the furnace; 200° C. (3 min.),30° C./min (4 min.), 320° C. (5 min.). The only drawing shows theresults obtained.

EXAMPLE 5 Formulation of an Acid Shampoo Using a Mixture with a Base of9-octadecenyl Betaine Mesylate

Mixture obtained in example 2 32 Diethylanolamide of copra 4Methylparaben 0.1 Propylparaben 0.1 Pale Morocco rose (rosa centifolia)0.5 Distilled water qsp 100 Citric acid qsp pH 5

EXAMPLE 6 Formulation of an Acid Shampoo Using a Mixture with a Base ofOctadecyl Betaine Mesylate

Mixture obtained in example 1, treatment C 18.75 Diethylanolamide ofcopra 4 Methylparaben 0.1 Propylparaben 0.1 Pale Morocco rose (rosacentifolia) 0.5 Distilled water qsp 100 Citric acid qsp pH 5

1. Surfactant composition comprising: at least one compound of formula(1)X⁻(CH₃)₃N⁺—CH₂—CO-Z-R  (1) and at least one compound selected from thosewith formulae (2), (3) and (4)RZH  (2)XH  (3)X⁻(CH₃)₃N⁺—CH₂—CO—OH  (4) X being a sulphonate radical, R being amonovalent radical of formula C_(2n)H_(2(2n−m)+1) containing 2n atoms ofcarbon and m double bonds, with 9≦n≦11, 0≦m≦3 if n=9 and 0≦m≦1 if n>9,and Z being selected from an atom of oxygen and a —NH— group, a compoundof formula XH being combined if necessary with at least one compound offormula RNH₂ in order to form at least one compound of formula X⁻RN⁺H₃.2. Composition according to claim 1, comprising virtually exclusivelycompounds of the said formulae (1), (2), (3) and (4).
 3. Compositionaccording to either of claims 1 or 2, wherein m=0 and the compoundsforming the composition are as follows, in the percentages by weightindicated: X⁻(CH₃)₃N⁺—CH₂—CO—O—R 50 ± 10 ROH 19 ± 10 XH 23 ± 10X⁻(CH₃)₃N⁺—CH₂—CO—OH 0 to
 18.


4. Composition according to either of claims 1 or 2, wherein m=0 and thecompounds forming the composition are the following, in the percentagesby weight indicated: X⁻(CH₃)₃N⁺—CH₂—CO—O—R 72 ± 10 ROH 0 to 20 XH 0 to18 X⁻(CH₃)₃N⁺—CH₂—CO—OH 0 to
 20.


5. Composition according to either of claims 1 or 2, wherein m=0 and thecompounds forming the composition are the following, in the percentagesby weight indicated: X⁻(CH₃)₃N⁺—CH₂—CO—O—R 80 ± 10 ROH 20 ±
 10.


6. Composition according to either of claims 1 or 2, wherein m=0 and thecompounds forming the composition are the following, in the percentagesby weight indicated: X⁻(CH₃)₃N⁺—CH₂—CO—O—R 70 ± 10 ROH 26 ± 10 XH 0 to14.


7. Composition according to either of claims 1 or 2, wherein m>0 and thecompounds forming the composition are the following, in the percentagesby weight indicated: X⁻(CH₃)₃N⁺—CH₂—CO—O—R 48 ± 10 ROH 36 ± 10 XH 14 ±10 X⁻(CH₃)₃N⁺—CH₂—CO—0H 0 to
 12.


8. Composition according to either of claims 1 or 2, wherein m=0 and thecompounds forming the composition are the following, in the percentagesby weight indicated: X⁻(CH₃)₃N⁺—CH₂—CO—NH—R 58 ± 10 X⁻RN⁺H₃ 35 ± 10X⁻(CH₃)₃N⁺—CH₂—CO—OH 0 to
 20.


9. Composition according to either of claims 1 or 2, wherein m>0 and thecompounds forming the composition are the following, in the percentagesby weight indicated: X⁻(CH₃)₃N⁺—CH₂—CO—NH—R 56 ± 10 X⁻RN⁺H₃ 31 ± 10 RNH₂0 to 18 X⁻(CH₃)₃N⁺—CH₂—CO—OH 0 to
 15.


10. Composition according to one of the preceding claims, wherein X isselected from the radicals methane sulphonate, paratoluene sulphonateand camphosulphonate.
 11. Method of preparing a composition according toeither of claims 1 or 2, wherein betaine glycine is reacted with asulphonic acid and a compound of the formula ROH in the absence of othersolvents, the molar ratio of sulphonic acid to betaine glycine beingcomprised between 2 and 3 and the molar ratio of the compound ROH to thebetaine glycine being between 1 and 1.5.
 12. Method according to claim11, wherein the reaction is carried out at a temperature of between 130and 140° C. for 6 to 8 hours.
 13. Method according to either of claims11 or 12, wherein the reaction is carried out under reduced pressure,preferably of between 50 and 100 mbar.
 14. Method according to one ofclaims 11 to 13, wherein m=0 and the reactional mixture is treated withan organic solvent capable of dissolving preferably the compounds otherthan the X⁻(CH₃)₃N⁺—CH₂—CO—O—R contained therein so as to obtain aprecipitate enriched in X⁻(CH₃)₃N⁺—CH₂—CO—O—R.
 15. Method according toclaim 14, wherein the organic solvent is selected from diethyl ether,ethanol and n-butanol.
 16. Method of preparing a composition accordingto either of claims 1 or 2, wherein betaine glycine is reacted with asulphonic acid and n-butanol in the absence of other solvents, the molarratio of the sulphonic acid to betaine glycine being between 1 and 1.3and the molar ration of the n-butanol to the betaine glycine beingbetween 2 and 4, in order to form water and the sulphonate of then-butylic ester of betaine glycine, which is reacted, after eliminationof the water and n-butanol, with the compound having the formula RNH₂,the molar ratio of this compound to betaine glycine being between 1 and1.2.
 17. Method according to claim 16, wherein the reaction of thebetaine glycine with the sulphonic acid and the n-butanol is carried outat a temperature of between 130 and 140° C., at the reflux of n-butanol,for 3 to 5 hours under atmospheric pressure so as to effect azeotropicelimination of water.
 18. Method according to one of claims 16 or 17,wherein, before the compound of formula RNH₂, is added a strong,encumbered organic base, in particular dibutylamine, the molar ratio ofthe base to the betaine glycine being between 0.1 and 0.4.
 19. Methodaccording to either of claims 16 to 18, wherein m=0 and the reactionalmixture is treated with an organic solvent capable of dissolvingpreferably the compound RNH₃ so as to obtain a precipitate enriched inX⁻ (CH₃)₃N⁺—CH₂—CO—NH—R.
 20. Method according to claim 19, wherein theorganic solvent is diethyl ether.
 21. Method according to one of claims11 to 20, wherein the sulphonic acid is selected from methanesulphonicacid, paratoluenesulphonic acid and camphosulphonic acid.
 22. Cosmetic,in particular liquid soap, foam bath, shower gel or shampoo and inparticular acid shampoo comprising 0.2 to 60% and preferably 10 to 45%by weight of a composition according to one of claims 1 to 10 and 99.8to 40% and preferably 90 to 55% by weight excipients appropriate forcosmetology.
 23. Cosmetic according to claim 22, wherein the excipientsare selected from thickeners, texturisers, conditioning agents,softeners, complexing agents, perfumes, pearlising agents,preservatives, acidifiers and purified water.
 24. Cosmetic according toclaim 23, wherein the excipients comprise as texturisers diethanolamidesof fatty acids, in particular diethanolamide of copra, with a contentnot exceeding 10% by weight of the cosmetic.